MODULE 5

Statistical

Mechanics
Gibss Free Energy

Prepared by: Group 4

 ΔG° = ΔH° - TΔS°

Gibbs Free

Energy
Energy that is available to do work
What is Gibbs Free Energy

Gibbs free energy (ΔG°) is a state function,

Gibbs free energy determines whether or
not a reaction is favorable or not. Gibbs free
energy is the energy associated with a
chemical reaction that is available to work.
 Gibbs Free Energy

Spontaneous Equilibrium Non Spontaneous

ΔG° = (-) ΔG° = 0 ΔG° = (+)

Do not required energy input State where no change of Require an energy input to
to proceed under a set of energy occur and stable. proceed and unfavourable.
conditions and favourable.
 Enthalpy (H°)
The variables

that affects the Entropy (S°)

Gibbs value
Temperature (K)
 Enthalpy

Enthalpy thermodynamic
quantity equivalent to the
total heat content of a
system.

ΔH > 0 (+ΔH) | ΔH < 0 (-ΔH)

Absorb heat | Release Heat
 Entropy

Entropy is a thermodynamic
quantity that measured
system's disorder

ΔS < 0 (-ΔS) | ΔS > 0 (+ΔS)

Less heat, Slower molecule | More heat, Faster molecule
Less movement | More movement
 Temperature

Temperature is the degree or

intensity of heat present in
a substance or object

ΔT > 0 (+T) | ΔT < 0 (-T)

Hotter | Colder
K = 273.15 + °C
 Temperature (T)
Enthalpy (ΔH°) Entropy (ΔS°)

Gibbs Free Energy

ΔG° = ΔH° - TΔS°

Spontaneous ΔG° = (-) Non Spontaneous ΔG° = (+)

Equilibrium ΔG° = 0
Determining Gibbs Free energy
Spontaneous or non spontaneous

(-) (+)

(+)

(-)
 Quadrant 1
Determining Gibbs Free energy ΔH° < 0 (-ΔH)
Spontaneous or non spontaneous ΔS° > 0 (+ΔH)
±T
____________________
Example
ΔH° = -119 kJ
ΔS° = 0.38 kJ/K
±T = 298 K
ΔG° = ΔH° - TΔS°
ΔG° = -119 kJ - (298K)(0.38 kJ/K)
ΔG° = - 119 kJ - 113.24 kJ
ΔG° = -232.24 kJ

Spontaneous reaction
 Quadrant 2
Determining Gibbs Free energy ΔH° > 0 (+ΔH)
Spontaneous or non spontaneous ΔS° > 0 (+ΔH)
T > 0 (+T)
____________________
Example
ΔH° = 75 kJ
ΔS° = 0.53 kJ/K
T = 311 K
ΔG° = ΔH° - TΔS°
ΔG° = 75 kJ - (311K)(0.53 kJ/K)
ΔG° = 75 kJ - 164 kJ
ΔG° = -89 kJ
Spontaneous reaction at
High Temperature
 Quadrant 3
Determining Gibbs Free energy ΔH° < 0 (-ΔH)
Spontaneous or non spontaneous ΔS° < 0 (-ΔH)
T < 0 (-T)
____________________
Example
ΔH° = -105 kJ
ΔS° = -0.765 kJ/K
T = -20 K
ΔG° = ΔH° - TΔS°
ΔG° = -105 kJ - (-20K)(-0.765 kJ/K)
ΔG° = - 105 kJ - 15.3 kJ
ΔG° = -120.3 kJ
Spontaneous reaction at
Low Temperature
 Quadrant 4
Determining Gibbs Free energy ΔH° < 0 (+ΔH)
Spontaneous or non spontaneous ΔS° > 0 (-ΔH)
±T
_________
Example
ΔH° = 149.4 kJ
ΔS° = -0.478 kJ/K
±T = 220 K
ΔG° = ΔH° - TΔS°
ΔG° = 149.4 kJ - (220K)(-0.478 kJ/K)
ΔG° = 149 kJ - (-105.16 kJ)
ΔG° = 254.16 kJ

Non spontaneous reaction

Gibbs Free Energy Table
(-) (+)

(+)

(-)
Example problem: Calculate the Gibbs free energy change (ΔG) for the
following chemical reaction: ATP ADP + Pi The reaction occurs at 27°C, the
change in heat (ΔH) = 764.24 kJ and the change in entropy (ΔS) = -25.8
kJ/K. Would be the reaction spontaneous?

Given:
Gibbs equation: ΔG° = ΔH° - TΔS°
(ΔH) = 764.24 kJ
(ΔS) = -25.8 kJ/K
T = 27°C = 300.15 K

Solution:
ΔG° = ΔH° - TΔS°
ΔG° = 764.24 kJ - (300.15 K)(-25.8kJ/K)
ΔG° = 764.24 kJ - (-738.369 kJ)
ΔG° = 1502.609 kJ ∴The reaction is not spontaneous
What is 2nd Law of

Thermodynamics?

The Second Law of Thermodynamics is about the quality of

energy. It states that as energy is transferred or
transformed, more and more of it is wasted. The Second Law
also states that there is a natural tendency of any isolated
system to degenerate into a more disordered state.


The
thermodynamic
The second law
arrow of time of
(entropy) is the thermodynamic
measurement of
disorder within a
s states that any
system. Denoted as spontaneously
ΔS, the change of occurring
entropy suggests
process will
that time itself is
asymmetric with always lead to
respect to order of an escalation in
an isolated system,
the entropy (S)
meaning: a system
will become more of the universe.
disordered, as time

increases.

2nd Law Equation

Mathematically, the second law of thermodynamics is represented as;

ΔSuniv > 0
where ΔSuniv is the change in the entropy of the universe.
Entropy is a measure of the randomness of the system or it is the measure of
energy or chaos within an isolated system. It can be considered as a
quantitative index that describes the quality of energy.
Meanwhile, there are few factors that cause an increase in entropy of the
closed system. Firstly, in a closed system, while the mass remains constant
there is an exchange of heat with the surroundings. This change in the heat
content creates a disturbance in the system thereby increasing the entropy of
the system.
Secondly, internal changes may occur in the movements of the molecules of
the system. This leads to disturbances which further causes irreversibilities
inside the system resulting in the increment of its entropy.
 There are two statements on
the second law of
Different thermodynamics which are:

Statements

of the Law 1. Kelvin- Planck Statement

2. Clausius Statement
Kelvin-Planck

Statement:
It is impossible for a heat
engine to produce a
network in a complete cycle
if it exchanges heat only
with bodies at a single fixed
temperature.
Clausius s ’
Statement:

It is impossible to construct a device

operating in a cycle that can transfer
heat from a colder body to warmer
without consuming any work.
 The Gibbs

Function as the

Driver to

Biophysical

Processes
 ATP

and

Free

Energy
 Understanding which chemical
reactions are spontaneous and

Why is it release free energy is extremely

useful for biologists because
these reactions can be harnessed
important to perform inside the cell.

The Gibbs free energy is

in important in biology research
because it enables one to predict
the direction of spontaneous
Biological change for a system under the
constraints of constant
system? temperature and pressure. These
constraints generally apply to all
living organisms.
ΔG∘(RXN)=ΣΔG∘F(PRODUCTS)
−ΣΔG∘F(REACTANTS)

standard Gibbs

Free Energy

GIBBS FREE ENERGY OF FORMATION

Standard Free Energy Changes

The standard Gibbs Free Energy is

calculated using the free energy of
formation of each component of a reaction
at standard pressure.
 Free energy of
formation:
The change of free energy that
accompanies the formation of
1 mole of a substance in its
standard state from its
constituent elements in their
standard states.
Reviewing Standard
States
Gases:
1 atmosphere partial pressure.
Pure liquids:
The liquid under a total pressure of 1 atm.
Solutes:
An effective concentration of 1 Molar.
Solids:
The pure solid under 1 atm pressure.
Note also that there is actually no “standard
temperature “, but because most
thermodynamics tables list values for 298.15
K (25° C), this temperature is usually
implied.
 Standard Free Energy Change
The sign of ΔG° predicts the behavior of a chemical reaction at the
standard conditions of 25°C and 1 atm of pressure. If ΔG° is negative,
the reaction will proceed spontaneously, if ΔG° is zero, the reaction
is at equilibrium, and if ΔG° is positive, the reaction will proceed
spontaneously in the reverse direction.

ΔG°rxn = ΣnΔG°f(products) – ΣnΔG°f(reactants)

Gibbs energy table value
Gibbs value varies depends on its
state of matter, its SI is kJ/mol but it
can also be expressed in kcal/mol

The conversion of unit of energy

Calories to Joule
1 Cal = 4.184 Joules
65 Cal x 4.184 J/Cal = 271.96 J

Joule to Calories
1 Joule = 0.239 Cal
272 Joule x 0.239 Cal/J = 65.01 Cal
Diatomic elements has zero free energy value
Remember that substances in elemental form (such as O2) have
ΔGfo values equal to zero.

Diatomic mol. mnemonic

Have No Fear Of Ice Cold Beer

Have - Hydrogen.
No - Nitrogen.
Fear - Fluorine.
Of - Oxygen.
Ice - Iodine.
Cold - Chlorine.
Beer - Bromine.
 Free energy value
H2(g) = 0 kJ/mol
O2(g) = 0 kJ/mol
H2O(g) = -228.59 kJ/mol

ΔG°rxn = ΣnΔG°f(products) – ΣnΔG°f(reactants)

Given:
ΣnΔG°f(products) = 2 H2O(g)
ΣnΔG°f(reactants) = 2 H2(g) + O2(g)
Solution:
ΔG°rxn=Σ[2ΔGf(H2O (g))] - Σ[2ΔGf(H2 (g)) + 1ΔGf(O2 (g))]
ΔG°rxn=Σ[2(-228.59kJ)] - Σ[2(0kJ) + 1(0kJ)] = -457.18 kJ
ΔG°rxn=(-457kJ) - (0kJ + 0kJ) = -457.18 kJ
ΔG°rxn=-457.18 kJ (spontaneous)
Example Problem: Calculate the value of ΔG°rxn

CO(g)+ 12O2(g) → CO2(g)

Gen eq: ΔG°rxn = ΣnΔG°f(products) – ΣnΔG°f(reactants)

Given: Free energy value

ΣnΔG°f(products) = 1 CO2(g) CO2(g) = −394.4 kJ kJ/mol
ΣnΔG°f(reactants) = 1 CO(g) + 12 O2(g) CO(g) = −137.2 kJ/mol
O2(g) = 0 kJ/mol
Solution:
ΔG°rxn=Σ[1ΔGf(CO2(g))] - Σ[1ΔGf(CO (g)) + 12ΔGf(O2 (g))]
ΔG°rxn=Σ[1(-394.4kJ)] - Σ[1(-137.2kJ) + 12(0kJ)] = -457.18 kJ
ΔG°rxn=(-394.4kJ) - (-137.2kJ + 0kJ) = -257.2 kJ
ΔG°rxn=-257.2 kJ (spontaneous)
Example Problem: Calculate the value of ΔG°rxn

H2O(l) → H2O(g)
Gen eq: ΔG°rxn = ΣnΔG°f(products) – ΣnΔG°f(reactants)

Free energy value

Given:
ΣnΔG°f(products) = 1 H2O (g) H2O (l) = -237.13 kJ/mol
ΣnΔG°f(reactants) = 1 H2O(l) H2O (g) = -228.6 kJ/mol

Solution:
ΔG°rxn=Σ[1ΔGf(H2O(g))] - Σ[1ΔGf(H2O (l))]
ΔG°rxn=Σ[1(-228.6kJ)]- Σ[1(-237.13kJ)]
ΔG°rxn=-228.6kJ - (-237.13kJ)
ΔG°rxn= 8.53 kJ (Not spontaneous)
Example Problem: Calculate the value of ΔG°rxn

CH4(g) + 2O2(g) → CO2(g) + 2H2O(l)

Gen eq: ΔG°rxn = ΣnΔG°f(products) – ΣnΔG°f(reactants)
Free energy value
Given:
ΣnΔG°f(products) = 1 CO2(g) + 2 H2O (l) CO2 (g) = −394.4 kJ kJ/mol
H2O (l) = -237.13 kJ/mol
ΣnΔG°f(reactants) = 1 CH4(g) + 2 O2(g)
CH4 (g) = -50.5 kJ/mol
O2 (g) = 0 kJ/mol
Solution:
ΔG°rxn=Σ[1ΔGf(CO2(g)) + [2ΔGf(H2O(l))] - Σ[1ΔGf(CH4 (g)) + 2ΔGf(O2 (g))]
ΔG°rxn=Σ[1(-394.4kJ)] + [2(-237.13kJ)]- Σ[1(-50.5kJ) + 2(0kJ)]
ΔG°rxn=(-394.4kJ + (-474.26kJ))- (-50.5kJ + 0kJ)
ΔG°rxn=-868.66kJ - (-50.5kJ)
ΔG°rxn=-818.16 kJ (spontaneous)
Thank you :>
Group 4
Group 4 Statistical Mechanics
Jinoel Matawaran
Cindirella Andrade
Aya Monique De Mesa

Sources
- https://docs.google.com/document/d/1xwS-
BPbGgS7J7xtCtIv0YSLle662PE9I-lWJuX-b-7o/edit
- https://www.ck12.org/book/ck-12-chemistry-
basic/section/20.2/
https://docs.google.com/document/d/1t2vrFhv8nImtju
NDt-qSbHYJ4NweOy6vqiWbtkF6MNE/edi